Photoresist topcoat for a photolithographic process

ABSTRACT

A composition that includes functionalized polyhedral oligomeric silsesquioxanes derivatives of the formulas T m   R3  where m is equal to 8, 10 or 12 and Q n M n   R1,R2,R3  where n is equal to 8, 10 or 12 are provided. The functional groups include aqueous base soluble moieties. Mixtures of the functionalized polyhedral oligomeric silsesquioxanes derivatives are highly suitable as a topcoat for photoresist in photolithography and immersion photolithography applications.

FIELD OF THE INVENTION

The present invention relates to the fields of non-polymer chemistry,photolithography and semiconductor fabrication; more specifically, itrelates to an composition of a non-polymeric, silicon-containingmaterial, a topcoat non-polymeric, silicon containing composition and amethod of forming a photolithographic image using the topcoat.

BACKGROUND OF THE INVENTION

As the size of structures of advanced integrated circuits has decreased,manufacturers are turning to a micro-lithography technique calledimmersion lithography, because of its improved resolution capability. Inimmersion lithography, an immersion fluid is placed between the opticallens and a photoresist layer. The immersion fluid provides considerablyhigher resolution than conventional photoirradiation in air. However, inmany photoresist systems, components of the photoresist leach out intothe immersion fluid and/or the immersion fluid penetrates into thephotoresist thus degrading performance. Therefore, there is a need for amethod to prevent interaction between photoresist layers and immersionfluid in an immersion lithography system.

SUMMARY OF THE INVENTION

The method to prevent interaction between photoresist layers andimmersion fluid in an immersion lithography system of the presentinvention is to apply a topcoat over a photoresist layer so the topcoatseparates the photoresist layer from the immersion fluid duringexposure. Topcoat compositions of the present invention are based onPolyhedral Oligomeric Silsesquioxanes derivatives that have the desiredattributes of being non-soluble in water (as many immersion fluidscomprise water), readily soluble in photoresist developer (particularlybasic developers), soluble in a casting solvent, not interacting withphotoresist (no dissolution, swelling of the photoresist due tointermixing), and low absorption at photoresist exposure wavelengths.

Further, the topcoat compositions of the present invention inhibitleaching of photoresist components into the immersion fluid.Additionally, the topcoat compositions of the present invention arenon-polymeric in nature.

A first aspect of the present invention is a resin composition,comprising: a Q_(n)M_(n) ^(R1,R2,R3) resin, wherein Q representsSiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³ SiO_(1/2), and n is equal to8, 10 or 12; wherein R¹ and R² are independently selected from the groupconsisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, abranched alkyl group having 2-12 carbon atoms, a cycloalkyl group having3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbonatoms, a fluorinated branched alkyl group having 2-12 carbon atoms, afluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkylsubstituted alkyl group having 4-23 carbon atoms and an alkylsubstituted cycloalkyl group having 4-23 carbon atoms; wherein R³ isselected from the group consisting of a linear alkyl group having 1-6carbon atoms, a branched alkyl group having 2-12 carbon atoms, acycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkylgroup having 2-12 carbon atoms, a fluorinated branched alkyl grouphaving 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbonatoms and an alkyl substituted cycloalkyl group having 4-23 carbonatoms; and wherein R³ includes either (a) a substituent Y¹ group and asubstituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y²are each selected from the group consisting of hydrogen, —COOH, —COOR¹—,—SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both behydrogen, and wherein Y³ is selected from the group consisting of—CONHCO— and —CONOHCO—, each monovalent bond of the Y³ group bonded todifferent adjacent carbon atoms of the R³.

A second aspect of the present invention is a resin composition,comprising: a T_(m) ^(R3) resin, wherein T represents R³ SiO_(3/2), andm is equal to 8, 10 or 12; wherein R³ is selected from the groupconsisting of a linear alkyl group having 1-6 carbon atoms, a branchedalkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms,a fluorinated branched alkyl group having 2-12 carbon atoms, and afluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkylsubstituted alkyl group having 4-23 carbon atoms and an alkylsubstituted cycloalkyl group having 4-23 carbon atoms; and wherein R³includes either (a) a substituent Y¹ group and a substituent Y² group or(b) a substituent Y³ group, wherein Y¹ and Y² are each selected from thegroup consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH,—NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both be hydrogen, andwherein Y³ is selected from the group consisting of —CONHCO— and—CONOHCO—, each monovalent bond of the Y³ group bonded to differentadjacent carbon atoms of the R³.

A third aspect of the present invention is a topcoat composition,comprising: a mixture of two or more resins, each resin of the mixtureof two or more resins comprising different Q_(n)M_(n) ^(R1,R2,R3)resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³SiO_(1/2), and n is equal to 8, 10 or 12; wherein R¹ and R² areindependently selected from the group consisting of hydrogen, a linearalkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinatedlinear alkyl group having 2-12 carbon atoms, a fluorinated branchedalkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl grouphaving 3-17 carbon atoms, a cycloalkyl substituted alkyl group having4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23carbon atoms; wherein R³ is selected from the group consisting of alinear alkyl group having 1-6 carbon atoms, a branched alkyl grouphaving 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, afluorinated linear alkyl group having 2-12 carbon atoms, a fluorinatedbranched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkylgroup having 3-17 carbon atoms, a cycloalkyl substituted alkyl grouphaving 4-23 carbon atoms and an alkyl substituted cycloalkyl grouphaving 4-23 carbon atoms; and wherein R³ includes either (a) asubstituent Y¹ group and a substituent Y² group or (b) a substituent Y³group, wherein Y¹ and Y² are each selected from the group consisting ofhydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, whereinY¹ and Y² cannot both be hydrogen, and wherein Y³ is selected from thegroup consisting of —CONHCO— and —CONOHCO—, each monovalent bond of theY³ group bonded to different adjacent carbon atoms of the R³; and acasting solvent selected from the group consisting of linearmonohydroxyl alcohols having 4-10 carbon atoms, branched chainmonohydroxyl alcohols having 4-10 carbon atoms, cyclic monohydroxylalcohols having 4-10 carbon atoms, linear dihydroxyl alcohols having4-10 carbon atoms, branched chain dihydroxyl alcohols having 4-10 carbonatoms, cyclic dihydroxyl alcohols having 4-10 carbon atoms, andcombinations thereof.

A fourth aspect of the present invention is a topcoat composition,comprising a mixture of two or more resins, each resin of the mixture oftwo or more resins comprising different T_(m) ^(R3) resins, wherein Trepresents R³ SiO_(3/2), and m is equal to 8, 10 or 12; wherein R³ isselected from the group consisting of a linear alkyl group having 1-6carbon atoms, a branched alkyl group having 2-12 carbon atoms, acycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkylgroup having 2-12 carbon atoms, a fluorinated branched alkyl grouphaving 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbonatoms and an alkyl substituted cycloalkyl group having 4-23 carbonatoms; and wherein R³ includes either (a) a substituent Y¹ group and asubstituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y²are each selected from the group consisting of hydrogen, —COOH, —COOR¹—,—SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both behydrogen, and wherein Y³ is selected from the group consisting of—CONHCO— and —CONOHCO—, each monovalent bond of the Y³ group bonded todifferent adjacent carbon atoms of the R³; and a casting solventselected from the group consisting of linear monohydroxyl alcoholshaving 4-10 carbon atoms, branched chain monohydroxyl alcohols having4-10 carbon atoms, cyclic monohydroxyl alcohols having 4-10 carbonatoms, linear dihydroxyl alcohols having 4-10 carbon atoms, branchedchain dihydroxyl alcohols having 4-10 carbon atoms, cyclic dihydroxylalcohols having 4-10 carbon atoms, and combinations thereof.

A fifth aspect of the present invention is a topcoat composition,comprising: a mixture of two or more different resins, wherein eachresin of the mixture of two or more different resins is selected fromthe group consisting of Q_(n)M_(n) ^(R1,R2,R3) resins and T_(m) ^(R3)resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³SiO_(1/2), n is equal to 8, 10 or 12, T represents R³ SiO_(3/2), and mis equal to 8, 10 or 12, wherein a first resin of the mixture of two ormore different resins is a Q_(n)M_(n) ^(R1,R2,R3) resin and a secondresin of the mixture of two or more different resins is a T_(m) ^(R3);wherein R¹ and R² are independently selected from the group consistingof hydrogen, a linear alkyl group having 1-6 carbon atoms, a branchedalkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms,a fluorinated branched alkyl group having 2-12 carbon atoms, afluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkylsubstituted alkyl group having 4-23 carbon atoms and an alkylsubstituted cycloalkyl group having 4-23 carbon atoms; wherein R³ isselected from the group consisting of a linear alkyl group having 1-6carbon atoms, a branched alkyl group having 2-12 carbon atoms, acycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkylgroup having 2-12 carbon atoms, a fluorinated branched alkyl grouphaving 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbonatoms and an alkyl substituted cycloalkyl group having 4-23 carbonatoms; and wherein R³ includes either (a) a substituent Y¹ group and asubstituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y²are each selected from the group consisting of hydrogen, —COOH, —COOR¹—,—SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both behydrogen, and wherein Y³ is selected from the group consisting of—CONHCO— and —CONOHCO—, each monovalent bond of the Y³ group bonded todifferent adjacent carbon atoms of the R³; and a casting solventselected from the group consisting of linear monohydroxyl alcoholshaving 4-10 carbon atoms, branched chain monohydroxyl alcohols having4-10 carbon atoms, cyclic monohydroxyl alcohols having 4-10 carbonatoms, linear dihydroxyl alcohols having 4-10 carbon atoms, branchedchain dihydroxyl alcohols having 4-10 carbon atoms, cyclic dihydroxylalcohols having 4-10 carbon atoms, and combinations thereof.

A sixth aspect of the present invention is a method of forming an imagein a photoresist layer, comprising: (a) providing a substrate; (b)forming the photoresist layer over the substrate; (c) forming a topcoatover a top surface of the photoresist layer, wherein the topcoat layerincludes at least one silicon containing material, includes no polymericmaterials, or includes at least one silicon containing material and nopolymeric materials; (d) exposing the photoresist to radiation through aphotomask having opaque and clear regions, the opaque regions blockingthe radiation and the clear regions being transparent to the radiation,the radiation changing the chemical composition of regions of thephotoresist layer exposed to the radiation forming exposed and unexposedregions in the photoresist layer; and (e) removing either the exposedregions of the photoresist layer or the unexposed regions of the layer.

BRIEF DESCRIPTION OF DRAWINGS

The features of the invention are set forth in the appended claims. Theinvention itself, however, will be best understood by reference to thefollowing detailed description of an illustrative embodiment when readin conjunction with the accompanying drawings, wherein:

FIG. 1 is a plot of contrast curves of a photoresist layer without atopcoat layer and a photoresist layer with a topcoat comprising theproduct of synthesis example 1 of the present invention;

FIG. 2A is a electron micrograph of a photoresist pattern formed in airwithout a topcoat;

FIG. 2B is a electron micrograph of a photoresist pattern formed in airwith a topcoat comprising the product of synthesis example 1 of thepresent invention;

FIG. 2C is a electron micrograph of a photoresist pattern formed underwater immersion with a topcoat comprising the product of synthesisexample 1 of the present invention;

FIG. 3A through 3C are partial cross-sectional views illustrating asemiconductor manufacturing process according to the present invention;and

FIG. 4 is a diagram of an exemplary immersion photolithographic systemthat may be used to process a semiconductor wafer having a topcoat layeraccording to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

An oligomer is defined as a molecule consisting of only a few, less thanabout 20, repeating units. The polyhedral silsesquioxane backbones ofthe Polyhedral Oligomeric Silsesquioxanes (POSS) derivatives of thepresent invention are thus oligmers of Si and O atoms with a smallnumber of repeating units (about 24 or less Si atoms). Furthermore, thePOSS derivatives themselves are not to be considered polymers, butrather monomers as there is only one non-repeating POSS unit in a POSSderivative of the present invention.

The POSS derivatives of the present invention are resins having thestructures (IA), (IB), (IIA), (IIIB), (IIIA) or (IIIB) where:

is denoted by the formula T₈ ^(R3), where T represents R³ SiO_(3/2).

is denoted by the formula Q₈M₈ ^(R1,R2,R3) where Q represents SiO_(4/2)and M^(R1,R2,R3) represents R¹,R²,R³SiO_(1/2);

is denoted by the formula T₁₀ ^(R3), where T represents R³ SiO_(3/2);

is denoted by the formula Q₁₀M₁₀ ^(R1,R2,R3) where Q representsSiO_(4/2) and M^(R1,R2,R3) represents R¹,R²,R³SiO_(1/2);

is denoted by the formula T₁₂ ^(R3), where T represents R³ SiO_(3/2);

is denoted by the formula Q₁₂M₁₂ ^(R1,R2,R3) where Q representsSiO_(4/2) and M^(R1,R2,R3) represents R¹,R²,R³SiO_(1/2);

wherein R¹ and R² are independently selected from the group consistingof hydrogen, a linear alkyl group having 1-6 carbon atoms, a branchedalkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms,a fluorinated branched alkyl group having 2-12 carbon atoms, afluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkylsubstituted alkyl group having 4-23 carbon atoms and an alkylsubstituted cycloalkyl group having 4-23 carbon atoms;

wherein R³ is selected from the group consisting of a linear alkyl grouphaving 1-6 carbon atoms, a branched alkyl group having 2-12 carbonatoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linearalkyl group having 2-12 carbon atoms, a fluorinated branched alkyl grouphaving 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbonatoms and an alkyl substituted cycloalkyl group having 4-23 carbonatoms; and

wherein R³ includes either (a) a substituent Y¹ group and a substituentY² group or (b) a substituent Y³ group, wherein Y¹ and Y² are eachselected from the group consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH,—C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both behydrogen, and wherein Y³ is selected from the group consisting of—CONHCO— and —CONOHCO—, each monovalent bond of the Y³ group bonded todifferent adjacent carbon atoms of the R³.

In the notation SiO_(x/y), x represents the number of oxygen atoms towhich each silicon atom is bonded and y represents the number of siliconatoms to which each oxygen is bonded. The POSS resins of the presentinvention may be denoted by the general formulas T_(m) ^(R3) where m isequal to 8, 10 or 12 and Q_(n)M_(n) ^(R1,R2,R3) where n is equal to 8,10 or 12.

It should also be noted that the notation Q_(n)M_(n) ^(R1,R2,R3) may bewritten as Q_(n)M_(n) ^(R2,R3) when R¹ is —CH₃, as Q_(n)M_(n)^(R1,R2,R3) when R² is —CH₃, as Q_(n)M_(n) ^(R3) when both R¹ and R² are—CH₃, as Q_(n)M_(n) ^(H,R2,R3) when R¹ is —H, as Q_(n)M_(n) ^(R1,H,R3)when R is —H, as Q_(n)M_(n) ^(H,H,R3) when both R¹ and R² are —H and asQ_(n)M_(n) ^(H,R3) when R¹ is —CH₃ and R² is H.

Synthesis of T_(m) ^(R3) and Q_(n)M_(n) ^(R1,R2,R3) Resins

Structure (IA) may be synthesized by reacting structure (IVA)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y group or a Y³ group(or a group that may be converted to a Y¹ group and/or a Y² group or aY³ group) in a suitable solvent and in the presence of a catalyst suchas platinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.

Structure (IB) may be synthesized by reacting structure (IVB)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y² group or a Y³ group(or a group that may be converted to a Y¹ group and/or a Y² group or aY³ group) in a suitable solvent and in the presence of a catalyst suchas platinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.

Structure (IIA) may be synthesized by reacting structure (VA)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y² group or a Y³ group(or a group that may be converted to a Y¹ group and/or a Y² group or aY³ group) in a suitable solvent and in the presence of a catalyst suchas platinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.

Structure (IIB) may be synthesized by reacting structure (VB)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y² group or a Y³ group(or a group that may be converted to a Y¹ group and/or a Y² group or aY³ group) in a suitable solvent and in the presence of a catalyst suchas platinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.Structure (IIIA) may be synthesized by reacting structure (VIA)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y² group or a Y³ group(or a group that may be converted to a Y¹ group and/or a Y² group or aY³ group) in a suitable solvent and in the presence of a catalyst suchas platinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.

Structure (IIIB) may be synthesized by reacting structure (VIIB)

with a substituted alkene or cylcoalkene, the substituent group being awater soluble moiety such as a Y¹ group and/or a Y² group or a Y³ group(or a group that may be converted to a Y group and/or a Y² group or a Y³group) in a suitable solvent and in the presence of a catalyst such asplatinum(0)-1,3-divinyl-1,1,3,3 tetramethyldisiloxane complex.

When either R¹, R² or both R¹ and R² are —H, the possibility exists ofmultiple additions of substituted alkene or cylcoalkene groups unlessthe substituted alkene or cylcoalkene groups are large enough tosterically hinder addition of more than one substituted alkene orcylcoalkene group. The scope of the present invention is intended tocover such multiple additions.

SYNTHESIS EXAMPLES

The silesesquioxane starting materials were purchased from TAL MaterialsInc., and Hybrid Plastics. Tetracyclo[4.4.0.1^(2,5).1^(7,12)]dodec-3-enestarting materials were obtained from JSR corporation. All the otherreagents were purchased from Aldrich Chemical Company. The products werecharacterized by NMR, IR, DSC, TGA, and GPC. The GPC traces of all theproducts showed a small shoulder on the high molecular weight side ofthe main peak. These are thought to be dimers formed during the reaction(J. V. Crivello, and R. Malik, “Synthesis and PhotoinitiatedPolymerization of Monomers with the Silsesquioxane Core”, J. Polym.Sci., Part A: Polymer Chemistry, Vol. 35, 407-425, (1997)). In somecases, the base soluble derivatives were synthesized in the castingsolvent and used as is.

Characterization of POSS resin performance was performed using a QuartzCrystal Microbalance (QCM) for dissolution properties, water uptake andfilm interaction studies. Lithographic behavior was evaluated using anISI Ultratech 193 nm 0.60 NA microstepper (dry exposure) and a 257 nminterferometer tool for water immersion experiments.

Example 1 Synthesis of a Carboxylic Acid/Ester POSS Derivative

Octakis(dimethylsilyloxy)silsesquioxane (Q₈M₈ ^(H)) (2.54 grams, 0.0025mole), cis-5-norbornene-endo-2,3-dicarboxylic anhydride (3.28 grams,0.020 mole), and tetrahydrofuran (THF) (20 ml) were placed in a roundbottom flask equipped with a magnetic stirrer, nitrogen inlet, and awater condensor. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxanecomplex in xylene (1 ml) was added to this mixture and stirred at roomtemperature for 1 hour and heated to reflux for 1 more hour. Accordingto the IR spectrum of the reaction product, the reaction was complete.The solvent was removed in a rotary evaporator and the residue was driedunder vacuum at room temperature. To the above solid, n-butanol (50grams), dimethylamino pyridine (DMAP) (50 milligrams) were added andheated to reflux for 1 hour. According to the IR spectrum of thereaction product, the reaction was complete. This solution was stirredwith amberlist 15 (washed, 2 grams) for 5 hours and filtered through a0.2 micron syringe filter.

Example 2 Synthesis of N-Hydoxyimide POSS Derivative

Octakis(dimethylsilyloxy)silsesquioxane (Q₈M₈ ^(H)) (2.0 grams, 0.002mole), endo-N-hydroxy-5-norbornene-2,3-dicarboximide (2.96 grams, 0.016mole)), and tetrahydrofuran (THF) (20 milliliters) were placed in around bottom flask equipped with a magnetic stirrer, nitrogen inlet, anda water condenser. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxanecomplex in xylene (1 ml) was added to this mixture and stirred at roomtemperature for 1 hour and heated to reflux for 1 more hour. Accordingto the IR spectrum of the reaction product, the reaction was complete.The reaction mixture was cooled to room temperature and added dropwiseinto hexane (400 milliliters). The solid was filtered through a fritfunnel, air dried for a 4 hours and then dried under vacuum at 55° C.,overnight (yield, 73%).

Example 3 Synthesis of Carboxylic Acid POSS Derivative

Octakis(dimethylsilyloxy)silsesquioxane (Q₈M₈ ^(H)) (0.57 grams, 0.00056mole), tetracyclo[4.4.0.1^(2,5).1^(7,12)]dodec-3-ene-5-carboxylic acid(0.92 gram, 0.0045 mole), and n-butanol (13.41 g) were placed in a roundbottom flask equipped with a magnetic stirrer, nitrogen inlet, and awater condenser. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxanecomplex in xylene (0.1 milliliter) was added to this mixture and stirredat room temperature for 24 hours and then at 30° C. for 1 hour.According to the IR spectrum of the reaction product, the reaction wascomplete. This solution was filtered through a 0.2 micron filter.

EXPERIMENTAL

FIG. 1 is a plot of contrast curves of a photoresist layer without atopcoat layer and a photoresist layer with a topcoat comprising theproduct of synthesis example 1 of the present invention. A 140 nm thicklayer of a commercial 193 nm (exposure wavelength) positive photoresist(Photoresist A) was formed on a first and second 5 inch silicon wafers,each having an anti-reflective coating (ARC). Both wafers were then postapply baked at 110° C. for 90 seconds. A 2% by weight solution of theproduct described in example 1 in n-butanol was used to form a topcoatover the photoresist layer of the first wafer. The photoresist layer ofthe second wafer of the photoresist wafers was left uncoated. Bothwafers were then baked at 120° C. for 60 seconds. Both wafers were thenblanket exposed in air (no mask) to create an array of exposure dosesfrom about 0 mJ/cm² to about 11.5 mJ/cm² at a wavelength of 193 nm. Thewafers were then post expose baked at 110° C. for 90 seconds. The waferswere then developed for 60 seconds in a 0.26 N tetramethyl ammoniumhydroxide (TMAH) developer. The thickness change of the photoresistlayers of both wafers versus exposure dose was measured and are plottedin FIG. 1. Curve 10 was obtained from the first (with a topcoat wafer)and contrast curve 20 was obtained from the second (non-coated) wafer.Contrast curves 10 and 20 are nearly identical indicating the absence ofany significant interference of the topcoat with the photoresistexposure/development system.

FIG. 2A is an electron micrograph of a photoresist pattern (130 nmlines/spaces) formed in air without a topcoat. A 140 nm thick layer of acommercial 193 nm (exposure wavelength) positive photoresist(Photoresist A) was formed on a first and second 5 inch silicon wafers,each having an anti-reflective coating (ARC). The wafer was post applybaked at 110° C. for 90 seconds. The wafer was then exposed in airthrough a 1:1 clear to opaque mask pattern at a wavelength of 193 nm andthen post expose baked at 110° C. for 90 seconds. The wafer wassubsequently developed for 60 seconds in 0.26 N TMAH developer.

FIG. 2B is a electron micrograph of a photoresist pattern (130 nmlines/spaces) formed in air with a topcoat comprising the product ofsynthesis example 1 of the present invention. A 140 nm thick layer of acommercial 193 nm (exposure wavelength) positive photoresist(Photoresist A) was formed on a 5 inch silicon wafer having ananti-reflective coating (ARC). The wafer was post apply baked at 110° C.for 90 seconds. A 2% by weight solution the product of synthesis example1 in n-butanol was used to form a topcoat over the photoresist layer ofthe wafer. The wafer was then exposed in air through a 1:1 clear toopaque mask pattern at a wavelength of 193 nm and then post expose bakedat 110° C. for 90 seconds. The wafer was subsequently developed for 60seconds in 0.26 N TMAH developer.

Comparing the electron micrograph of FIG. 2A to the electron micrographof FIG. 2B illustrates that the photoresist image formed from thephotoresist layer that had a topcoat (FIG. 2B) had comparable image tothe image formed from the photoresist layer that was did not have atopcoat (FIG. 2A). In fact, improved performance can be observed in thatthe photoresist layer having a topcoat had a squarer photoresist profilewith less rough edges and less thickness loss than the photoresist layerwithout a topcoat.

FIG. 2C is a electron micrograph of a photoresist pattern (90 nmlines/spaces) formed under water immersion with a topcoat comprising theproduct of synthesis example 1 of the present invention. A 140 nm thicklayer of a commercial 193 nm (exposure wavelength) positive photoresist(Photoresist A) was formed on a 5 inch silicon wafer having an ARC. Thewafer was post apply baked at 110° C. for 90 seconds (PAB). A 2% byweight solution the product of synthesis example 1 in n-butanol was usedto form a topcoat over the photoresist layer of the wafer. The wafer wasthen exposed under water immersion using 257 nm interference lithographyand then post expose baked at 110° C. for 90 seconds. The wafer wassubsequently developed for 60 seconds in 0.26 N TMAH developer. Thephotoresist images of FIG. 3C demonstrate the utility of the product ofexample 1 as a topcoat material for immersion lithography.

Process Methodology and Tooling

FIG. 3A through 3C are partial cross-sectional views illustrating asemiconductor manufacturing process according to the present invention.In FIG. 3A, a substrate 30 is provided. In one example, substrate 30 isa semiconductor substrate. Examples of semiconductor substrates includebut are not limited to bulk (single crystal) silicon wafers and siliconon insulator (SOI) wafers. Formed on a top surface 35 of substrate 30 isan optional ARC 40. In one example, ARC 40 is spin applied and a postARC apply bake (heated above room temperature to remove most of the ARCsolvent) performed. Formed on a top surface 45 of ARC 40 is aphotoresist layer 50. In one example, photoresist layer 50 is spinapplied and a post photoresist apply bake, also known as a pre-exposuresbake or a pre-bake (heated above room temperature to remove most of thephotoresist solvent) performed. Next a topcoat 60 is formed on a topsurface 55 of photoresist layer 50. In one example, topcoat 60 is spinapplied and a post topcoat apply bake (heated above room temperature toremove most of the topcoat solvent) performed. Topcoat 60 comprises asingle T_(m) ^(R3) resin, multiple different T_(m) ^(R3) resins, asingle Q_(n)M_(n) ^(R1,R2,R3) resin, multiple different Q_(n)M_(n)^(R1,R2,R3) resins or a mixture of one or more different T_(m) ^(R3)resins and one or more different Q_(n)M_(n) ^(R1,R2,R3) resins asdescribed supra.

In FIG. 3B, a layer of immersion fluid 70 is formed over a top surface75 of topcoat 60 in a immersion photolithography tool (see FIG. 4 anddescription infra). An example of an immersion fluid is water, with orwithout additives. Light of a wavelength that photoresist layer 50 issensitive to is passed through a photomask 80. Photo mask 80 has clearregions 85 that transmit the light and opaque regions 90 that block thelight. Exposure of photoresist layer 50 to light through mask 80 formsunexposed regions 95A of photoresist layer 50 and exposed regions 95B ofphotoresist layer 50. Exposed regions 95B are also known as latent imageregions. An optional post exposure bake (heated above room temperatureto drive the photoresist chemistry) may be performed.

Although a positive photoresist is shown in FIG. 3B, the presentinvention works equally well with negative photoresist systems or dualtone photoresist systems. In negative photoresist systems, thephotoresist will develop away where it is not exposed to light, so aphotomask of polarity opposite to that illustrated in FIG. 3B isrequired. Dual tone resists can act either negatively or positivelydepending upon the developer system used.

In FIG. 3C, substrate 30 is removed from the immersion photolithographytool and photoresist layer 50 developed to remove exposed regions 95B(see FIG. 3B) and leave behind unexposed regions 95A. In one example thedeveloper comprises an aqueous solution of a base such as TMAH. Topcoat60 (see FIG. 3B) is also removed by the developer. Optionally, topcoatlayer 60 may be removed separately prior to development of the exposedphotoresist layer 50. An optional post development bake, (heated aboveroom temperature to harden the photoresist images) may be performed.

While the exposure of the photoresist layer was described in the contextof an immersion photolithography system, the topcoat compositions of thepresent invention also have utility in conventional (non-immersion)photolithography system as illustrated by the comparison of FIGS. 2A and2B described supra as a protective coating against environmentalcontamination from particulates, water vapor, and chemical vapors thatcould degrade the imaging process or cause imperfections in thephotoresist images and ultimately yield or reliability defects in thefabricated product.

FIG. 4 is a diagram of an exemplary immersion photolithographic systemthat may be used to process a semiconductor wafer having a topcoat layeraccording to the present invention. In FIG. 4, an immersion lithographysystem 100 includes a controlled environment chamber 105 and acontroller 110. Contained within controlled environment chamber 105 is afocusing mirror 115, a light source 120, a first focusing lens (or setof lenses) 125, a mask 130, an exposure slit 135, a second focusing lens(or set of lenses) 140, a final focusing lens 145, an immersion head 150and a wafer chuck 155. Immersion head 150 includes a transparent window160, a central chamber portion 165, a surrounding plate portion 170, animmersion fluid inlet 175A and an immersion fluid outlet 175B. Animmersion fluid 185 fills central chamber portion 165 and contacts aphotoresist layer 186 on a top surface 188 of a wafer 190, and thephotoresist layer 186 includes a topcoat formed of a POSS derivativeresin or mixture of POSS derivative resins according to the presentinvention. Alternatively, wafer 190 may have an ARC formed on topsurface 188 and photoresist layer 186 is then be formed on a top surfaceof the ARC. In one example, immersion fluid 185 includes water. Plateportion 170 is positioned close enough to photoresist layer 186 to forma meniscus 192 under plate portion 170. Window 160 must be transparentto the wavelength of light selected to expose photoresist layer 186.

Focusing mirror 115, light source 120, first focusing lens 125, a mask130, exposure slit 135, second focusing lens 140, final focusing lens145, immersion head 150 are all aligned along an optical axis 200 whichalso defines a Z direction. An X direction is defined as a directionorthogonal to the Z direction and in the plane of the drawing. A Ydirection is defined as a direction orthogonal to both the X and Zdirections. Wafer chuck 155 may be moved in the X and Y directions underthe direction of controller 110 to allow formation of regions of exposedand unexposed photoresist in photoresist layer 186. As an XY-stagemoves, new portions of photoresist layer 186 are brought into contactwith immersion fluid 185 and previously immersed portions of thephotoresist layer are removed from contact with the immersion fluid.Mask 130 and slit 135 may be moved in the Y direction under the controlof controller 110 to scan the image (not shown) on mask 130 ontophotoresist layer 186. In one example, the image on mask 130 is a 1× toa 10× magnification version of the image to be printed and includes oneor multiple integrated circuit chip images.

When exposure is complete, wafer 190 is removed from controlledenvironment chamber 105 without spilling immersion fluid 185. To thisend, controlled environment chamber 105 also includes a cover plate 195that may be moved to first abut with wafer chuck 155 and then moved withthe wafer chuck as the wafer chuck is moved out of position from underimmersion head 150, the cover plate replacing the wafer chuck underimmersion head 150.

The topcoat compositions of the present invention may be used with othertypes of immersion lithography tools and example of which is animmersion lithography tool wherein the immersion fluid is dispensed ontothe wafer from openings in the lens barrel surrounding the lens.

The description of the embodiments of the present invention is givenabove for the understanding of the present invention. It will beunderstood that the invention is not limited to the particularembodiments described herein, but is capable of various modifications,rearrangements and substitutions as will now become apparent to thoseskilled in the art without departing from the scope of the invention.Therefore it is intended that the following claims cover all suchmodifications and changes as fall within the true spirit and scope ofthe invention.

1. A method of forming an image in a photoresist layer, comprising: (a) providing a substrate; (b) forming said photoresist layer over said substrate; (c) forming a topcoat over said photoresist layer, wherein said topcoat layer comprises a polyhedral oligomeric silsesquioxane based material, said polyhedral oligomeric silsesquioxane based material including an aqueous base soluble functional group; (d) exposing said photoresist to radiation through a photomask having opaque and clear regions, said opaque regions blocking said radiation and said clear regions being transparent to said radiation, said radiation changing the chemical composition of regions of said photoresist layer exposed to said radiation forming exposed and unexposed regions in said photoresist layer; and (e) removing either said exposed regions of said photoresist layer or said unexposed regions of said layer.
 2. The method of claim 1, further including, between (a) and (b), forming an anti-reflective coating over a top surface of said substrate, wherein said photoresist layer is formed on a top surface of said anti-reflective coating.
 3. The method of claim 1, further including, between (c) and (d), forming a layer of immersion fluid between said topcoat layer and said photomask.
 4. The method of claim 3, wherein said immersion fluid includes water.
 5. The method of claim 1, wherein (e) further includes removing said topcoat layer.
 6. The method of claim 1, further including, between (c) and (d), removing a casting solvent from said topcoat layer.
 7. The method of claim 1, further including, between (c) and (d), heating said topcoat to a temperature above room temperature.
 8. The method of claim 1, wherein said topcoat layer does not include materials containing fluorine.
 9. The method of claim 1, wherein said topcoat layer comprises: one or more resins, each resin of said one or more resins selected from the group consisting of Q_(n)M_(n) ^(R1,R2,R3) resins and T_(m) ^(R3) resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³ SiO_(1/2), n is equal to 8, 10 or 12, T represents R³ SiO_(3/2), and m is equal to 8, 10 or 12; wherein R¹ and R² are independently selected from the group consisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ is selected from the group consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; and wherein R³ includes either (a) a substituent Y¹ group and a substituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y² are each selected from the group consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both be hydrogen, and wherein Y³ is selected from the group consisting of —CONHCO— and —CONOHCO—, each monovalent bond of said Y³ group bonded to different adjacent carbon atoms of said R³; and a casting solvent selected from the group consisting of a linear monohydroxyl alcohol having 4-10 carbon atoms, a branched chain monohydroxyl alcohol having 4-10 carbon atoms, a cyclic monohydroxyl alcohol having 4-10 carbon atom, a linear dihydroxyl alcohol having 4-10 carbon atoms, a branched chain dihydroxyl alcohol having 4-10 carbon atoms, a cyclic dihydroxyl alcohol having 4-10 carbon atoms, and combinations thereof.
 10. A method of forming an image in a photoresist layer, comprising: (a) providing a substrate; (b) forming said photoresist layer over said substrate; (c) forming a topcoat over said photoresist layer, wherein said topcoat layer comprises a polyhedral oligomeric silsesquioxane based material, said polyhedral oligomeric silsesquioxane based material includes an aqueous base soluble functional group; (d) exposing said photoresist to radiation through a photomask having opaque and clear regions, said opaque regions blocking said radiation and said clear regions being transparent to said radiation, said radiation changing the chemical composition of regions of said photoresist layer exposed to said radiation forming exposed and unexposed regions in said photoresist layer; and (e) removing either said exposed regions of said photoresist layer or said unexposed regions of said layer; and wherein said topcoat layer comprises: a casting solvent selected from the group consisting of a linear monohydroxyl alcohol having 4-10 carbon atoms, a branched chain monohydroxyl alcohol having 4-10 carbon atoms, a cyclic monohydroxyl alcohol having 4-10 carbon atom, a linear dihydroxyl alcohol having 4-10 carbon atoms, a branched chain dihydroxyl alcohol having 4-10 carbon atoms, a cyclic dihydroxyl alcohol having 4-10 carbon atoms, and combinations thereof; one or more resins, each resin of said one or more resins selected from the group consisting of Q_(n)M_(n) ^(R1,R2,R3) resins and T_(m) ^(R3) resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³ SiO_(1/2), n is equal to 8, 10 or 12, T represents R³ SiO_(3/2), and m is equal to 8, 10 or 12; wherein R¹ and R² are independently selected from the group consisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ is selected from the group consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ includes either (a) a substituent Y¹ group and a substituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y² are each selected from the group consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹,—NHCOR¹, wherein Y¹ and Y² cannot both be hydrogen, and wherein Y³ is selected from the group consisting of —CONHCO— and —CONOHCO—, each monovalent bond of said Y³ group bonded to different adjacent carbon atoms of said R³; and wherein R³ of at least one resin of said one or more resins is represented by the formula:


11. The method of claim 10, wherein Y¹ is —COO(CH₂)₃CH₃ and Y² is—COOH.
 12. A method of forming an image in a photoresist layer, comprising: (a) providing a substrate; (b) forming said photoresist layer over said substrate; (c) forming a topcoat over said photoresist layer, wherein said topcoat layer comprises a polyhedral oligomeric silsesquioxane based material, said polyhedral oligomeric silsesquioxane based material includes an aqueous base soluble functional group; (d) exposing said photoresist to radiation through a photomask having opaque and clear regions, said opaque regions blocking said radiation and said clear regions being transparent to said radiation, said radiation changing the chemical composition of regions of said photoresist layer exposed to said radiation forming exposed and unexposed regions in said photoresist layer; and (e) removing either said exposed regions of said photoresist layer or said unexposed regions of said layer; and wherein said topcoat layer comprises: a casting solvent selected from the group consisting of a linear monohydroxyl alcohol having 4-10 carbon atoms, a branched chain monohydroxyl alcohol having 4-10 carbon atoms, a cyclic monohydroxyl alcohol having 4-10 carbon atom, a linear dihydroxyl alcohol having 4-10 carbon atoms, a branched chain dihydroxyl alcohol having 4-10 carbon atoms, a cyclic dihydroxyl alcohol having 4-10 carbon atoms, and combinations thereof; one or more resins, each resin of said one or more resins selected from the group consisting of Q_(n)M_(n) ^(R1,R2,R3) resins and T_(m) ^(R3) resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³ SiO_(1/2), n is equal to 8, 10 or 12, T represents R³ SiO_(3/2), and m is equal to 8, 10 or 12; wherein R¹ and R² are independently selected from the group consisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ is selected from the group consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ includes either (a) a substituent Y¹ group and a substituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y² are each selected from the group consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both be hydrogen, and wherein Y³ is selected from the group consisting of —CONHCO— and —CONOHCO—, each monovalent bond of said Y³ group bonded to different adjacent carbon atoms of said R³; and wherein R³ of at least one resin of said one or more resins is represented by the formula:


13. The method of claim 12, wherein Y¹ is —COOH and Y² is —H.
 14. A method of forming an image in a photoresist layer, comprising: (a) providing a substrate; (b) forming said photoresist layer over said substrate; (c) forming a topcoat over said photoresist layer, wherein said topcoat layer comprises a polyhedral oligomeric silsesquioxane based material, said polyhedral oligomeric silsesquioxane based material includes an aqueous base soluble functional group; (d) exposing said photoresist to radiation through a photomask having opaque and clear regions, said opaque regions blocking said radiation and said clear regions being transparent to said radiation, said radiation changing the chemical composition of regions of said photoresist layer exposed to said radiation forming exposed and unexposed regions in said photoresist layer; and (e) removing either said exposed regions of said photoresist layer or said unexposed regions of said layer; and wherein said topcoat layer comprises: a casting solvent selected from the group consisting of a linear monohydroxyl alcohol having 4-10 carbon atoms, a branched chain monohydroxyl alcohol having 4-10 carbon atoms, a cyclic monohydroxyl alcohol having 4-10 carbon atom, a linear dihydroxyl alcohol having 4-10 carbon atoms, a branched chain dihydroxyl alcohol having 4-10 carbon atoms, a cyclic dihydroxyl alcohol having 4-10 carbon atoms, and combinations thereof; one or more resins, each resin of said one or more resins selected from the group consisting of Q_(n)M_(n) ^(R1,R2,R3) resins and T_(m) ^(R3) resins, wherein Q represents SiO_(4/2), M^(R1,R2,R3) represents R¹,R²,R³ SiO_(1/2), n is equal to 8, 10 or 12, T represents R³ SiO_(3/2), and m is equal to 8, 10 or 12; wherein R¹ and R² are independently selected from the group consisting of hydrogen, a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ is selected from the group consisting of a linear alkyl group having 1-6 carbon atoms, a branched alkyl group having 2-12 carbon atoms, a cycloalkyl group having 3-17 carbon atoms, a fluorinated linear alkyl group having 2-12 carbon atoms, a fluorinated branched alkyl group having 2-12 carbon atoms, a fluorinated cycloalkyl group having 3-17 carbon atoms, a cycloalkyl substituted alkyl group having 4-23 carbon atoms and an alkyl substituted cycloalkyl group having 4-23 carbon atoms; wherein R³ includes either (a) a substituent Y¹ group and a substituent Y² group or (b) a substituent Y³ group, wherein Y¹ and Y² are each selected from the group consisting of hydrogen, —COOH, —COOR¹—, —SO₂OH, —C(CF₃)₂OH, —NHSO₂R¹, —NHCOR¹, wherein Y¹ and Y² cannot both be hydrogen, and wherein Y³ is selected from the group consisting of —CONHCO— and —CONOHCO—, each monovalent bond of said Y³ group bonded to different adjacent carbon atoms of said R³; and wherein R³ of at least one resin of said one or more resins is represented by the formula: 